Previously known oxidative dehydrogenation processes for producing butadiene from hydrocarbons have used natural gas fired heaters to vaporize and superheat the reaction feed streams and consequently have produced emissions, particularly CO2 emissions, far in excess of the level acceptable in today's climate. In particular, previous processes typically used natural gas to vaporize butene and heat a mixture of hydrocarbons, preferably butenes, oxygen and steam to a temperature in excess of 260° C. (500° F.), more commonly in excess of about 315° C. (600° F.), and preferably over about 345° C. (650° F.) or, in some cases, even over 371° C. (700° F.). In a typical process, the reaction mixture includes butenes, oxygen in an amount of from about 0.4 moles to about 0.8 moles, more typically from slightly in excess of 0.5 moles up to about 0.65 moles of oxygen for each mole of butene in the butene rich hydrocarbonaceous feed, and superheated steam in amounts of from about 12:1 to about 16:1. Subsequent to reaction, the reaction product mixture is cooled and butadiene separated by oil absorption and subsequent fractionation. Typically, these processes produce crude butadiene at a purity ranging from about 50 to about 70%, more typically from about 55 to about 65%, which is passed onward in the plant for further processing using known technologies.
References of interest are discussed below.
Lewis; HYDROCARBON CONVERSION PROCESS USING NOVEL METALLO MANGANESE OXIDES; U.S. Pat. No. 5,772,898; Jun. 30, 1998; relates to a hydrocarbon conversion process comprising contacting a hydrocarbon feed with a catalyst comprising a crystalline metallo manganese oxide composition having a three-dimensional framework structure, an intracrystalline pore system and an empirical chemical composition on an anhydrous basis expressed by the formula:AyMn8-xMxO16 
where A is a templating agent selected from alkali metals, alkaline earth metals and ammonium ion, “y” is the moles of A and varies from the group consisting of about 0.5 to about 2.0, M is a metal selected from the group consisting of chromium, zirconium, tin, platinum, rhodium, niobium, tantalum, vanadium, antimony, ruthenium, gallium and germanium, “x” is the moles of M and varies from about 0.01 to about 4.0 and characterized in that manganese has a valence of +3, or +4, M has a valence of +3, +4 or +5 and the composition has the hollandite structure.
Sasaki et al.; IRON-ANTIMONY-CONTAINING METAL OXIDE CATALYST COMPOSITION AND PROCESS FOR PRODUCING THE SAME; U.S. Pat. No. 5,139,988; Aug. 18, 1992; relates to a composition which contains as essential components: crystalline iron antimonate and at least one element selected from the group consisting of vanadium, molybdenum, and tungsten; is useful as a catalyst in the oxidation reaction of organic compounds. Also, a process for producing the composition is disclosed.
Dejaifve et al.; CATALYST FOR DEHYDROGENATING ORGANIC COMPOUNDS, A PROCESS FOR ITS PREPARATION AND ITS USE; U.S. Pat. No. 4,975,407; Dec. 4, 1990; relates to a catalyst derived from iron oxides providing agents and potassium oxide providing agents, characterized in that the molar ratio is in the range of from 1.5 to 60 and that a potassium ferrite K2Fe12O19 phase is present supported on an octahedral Fe3O4 matrix, showing crystalline epitaxy between the hexagonal structure of K2Fe12O19 and the (111) planes of the Fe3O4 spinel structure.
McFarland; OXIDATIVE DEHYDROGENATION OF AMYLENES; U.S. Pat. No. 4,973,793; Nov. 27, 1990; relates to an oxidative dehydrogenation process wherein butylenes are cofed with amylenes in a catalytic oxidative dehydrogenation reaction which is said to substantially improve the conversion of the amylenes. The improved amylene conversion is obtained by the oxidative dehydrogenation of mixtures of amylenes and from 10 to 95 mole % butylenes.
Heiberg, U.S. Pat. No. 4,067,921, discloses heat recovery in connection with a butadiene production operation. See FIG. 4 and the text at Col. 6, lines 20-38.
Miklas, METHOD OF ACTIVATING ZINC-FERRITE OXIDATIVE DEHYDROGENATION CATALYST; U.S. Pat. No. 3,953,370; Apr. 27, 1976, relates to use of steam at a temperature of from 370-700° C. (700-1300° F.) to activate a zinc ferrite oxidative dehydrogenation catalyst for preparation of butadiene from C4-C8 hydrocarbons.
Tschopp; DIOLEFIN PRODUCTION AND PURIFICATION; U.S. Pat. No. 3,943,185; Mar. 9, 1976 relates to a process for producing a stream of oxidatively dehydrogenated C4 hydrocarbons substantially free of oxygen and inert noncondensable gases removed comprising absorbing the C4 hydrocarbons in an absorber oil in a first zone; stripping oxygen and inert noncondensable gases from the mixture of adsorber oil and C4 hydrocarbons in a second zone which is operated under conditions of temperature and pressure to maintain an aqueous phase in the second zone; and withdrawing (1) a predominately aqueous phase from the second zone, (2) an overhead of predominately all of the oxygen and inert noncondensable gases and a bottoms of adsorber oil and C4 hydrocarbon substantially free of oxygen and inert noncondensable gases.
In Croce et al.; SULFUR PROMOTED OXIDATIVE DEHYDROGENATION; U.S. Pat. No. 3,937,746; Feb. 10, 1976; the yield in oxidative dehydrogenation of organic compounds is improved by having a sulfur promoter present either as part of the catalyst or added to the reaction with the reactants.
In Marsheck; OXIDATIVE DEHYDROGENATION OF ORGANIC COMPOUNDS; U.S. Pat. No. 3,801,671; Apr. 2, 1974; it is reported that the oxidative dehydrogenation of paraffinic hydrocarbons to diolefins can be improved by effecting such dehydrogenation in the presence of a fluidized mixed catalyst system consisting essentially of at least one catalyst active for the conversion of paraffins in admixture with at least one catalyst active for the conversion of monoolefins.
In Bertus, et al.; OXIDATIVE DEHYDROGENATION OF PARAFFINIC HYDROCARBONS; U.S. Pat. No. 3,745,194; Jul. 10, 1973; organic compounds are dehydrogenated to compounds having a higher degree of unsaturation by contacting the feedstock in the vapor phase in the presence of an oxygen containing gas with a catalyst containing tin in an oxidized state in combination with at least one of the metals bismuth, cobalt, or nickel in an oxidized state. Representative of such conversions is the oxidative dehydrogenation of butane to 1,3-butadiene over a nickel stannate-containing catalyst.
In Woerner et al; PURIFICATION OF UNSATURATED HYDROCARBONS BY EXTRACTIVE DISTILLATION WITH ADDITION OF LIQUID SOLVENT To STRIPPER OVERHEAD; U.S. Pat. No. 3,496,070; Feb. 17, 1970, a hydrocarbon separation process is provided for the separation of a hydrocarbon mixture comprising 4 to 5 carbon atoms including unsaturated hydrocarbons which comprises: extractively distilling the hydrocarbon mixture with a selective solvent in an extractive distillation column whereby hydrocarbon is selectively extracted in the extractive distillation column to form a hydrocarbon-rich solvent fraction which is fed to a solvent stripping column with said solvent being taken off as a bottoms from said stripping column and a vaporous hydrocarbon fraction being taken as an overhead fraction from said stripping column; adding said selective solvent in liquid phase to the vaporous overhead from the solvent stripper to lower the pressure in the overhead condenser of the solvent stripper column and in the solvent stripper.
Bajars; DEHYDROGENATION WITH MAGNESIUM FERRITE; U.S. Pat. No. 3,284,536; Nov. 8, 1966 relates to dehydrogenating hydrocarbons in the vapor phase at elevated temperatures in the presence of oxygen and a catalyst containing magnesium ferrite. Hydrocarbons to be dehydrogenated according to the process are hydrocarbons of 4 to 7 carbon atoms, preferably aliphatic hydrocarbons selected from the group consisting of saturated hydrocarbons, monoolefins, diolefins and mixtures thereof of 4 to 5 or 6 carbon atoms having a straight chain of at least four carbon atoms, and cycloaliphatic hydrocarbons. Oxygen is present in the reaction zone in an amount within the range of 0.2 to 2.5 mols of oxygen per mol of hydrocarbon to be dehydrogenated. The temperature for the dehydrogenation reaction will be greater than 250° C., such as greater than about 300° C. or 375° C., and the maximum temperature in the reactor may be about 650° C. or 750° C. or perhaps higher under certain circumstances.
Gay; DEHYDROGENATION IN THE PRESENCE OF OXYGEN AND AN AMMONIUM HALIDE; U.S. Pat. No. 3,207,805; Sep. 21, 1965 relates to a process for dehydrogenating organic compounds and relates more particularly to the dehydrogenation of dehydrogenatable organic compounds at elevated temperatures in the presence of oxygen and an ammonium halide.
Welch, et al., in “BUTADIENE VIA OXIDATIVE DEHYDROGENATION”, Hydrocarbon Processing, November 1978, pp. 131-136; discuss an oxidative dehydrogenation process, in which steam, air or oxygen, and normal butenes are heated and passed over an undisclosed autoregenerative heterogeneous catalyst at around 430° C. (800° F.) using steam as a heat sink to moderate the temperature rise in the adiabatic reactor system without using gas phase additives such as halogen and sulfur compounds. The process is said to consume essentially all of the oxygen in the feed usually leaving oxygen levels in the effluent below 0.3 percent. Acetylenes and oxygenated byproducts are major by products.